the most common scenario to see this happen is: an incoming email is (automatically) forwarded from anothe email address for the same recipient, and the email is replied by REPLY ALL.

for example, say your name is Zero Kool, you got two email addresses zkool@domain1.com and zkool@domain2.com and the two mailboxes are jointed with each other, which means any email sent to domain1 box will be automatically forwarded to domain2 box, and vice versa. you, for some reasons, always use the second mailbox on your iPhone.

say the following email has been sent to you and you received the forwarded copy on your iPhone. if you are going to reply it using the iPhone, the story will start.

There are two problems happening here, 2 accounts are configured on his iPhone, when he goes to the 'FROM' field, it does not default to the exchange SMTP email address, another proxy address pops up, NOT his primary SMTP email address.
When he picks that, and then sends the email, it 'cc's' a copy to the primary SMTP email address.

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